TW201136910A - Aminoanthracene derivative and organic electroluminescent element formed using same - Google Patents

Abstract

Provided is an aminoanthracene derivative represented by formula (1) and having an end substituent, e.g., a dibenzofuran ring, bonded in a position other than the 2-position to the anthracene through a nitrogen atom. Also provided is an organic electroluminescent element which comprises a cathode and an anode and, disposed therebetween, one or more organic thin film layers comprising a luminescent layer, at least one of the organic thin film layers containing the aminoanthracene derivative. The organic electroluminescent element has a long life and a high luminescent efficiency. [In formula (1), R1, m, and Ar1 to Ar4 have the meanings described in claim 1.]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amine-based fluorene derivative and an organic electroluminescent device using the same, and more particularly to an organic electroluminescent device having an odd-term long-term luminous efficiency and The amine hydrazine derivative obtained therefrom is obtained. [Prior Art] An organic electroluminescence (EL) element using an organic substance is expected to be used for the development of a large-area full-color display element of a solid-emitting type. Usually, the 'organic EL element' is composed of a light-emitting layer and a counter electrode sandwiching one of the layers. The phenomenon of luminescence is as follows: if an electric field is applied between the electrodes, electrons are injected from the cathode side, and holes are injected from the anode side; further, the electrons are recombined with the holes in the luminescent layer to generate an excited state, and the excited state returns to the base. In the state, energy is released as light. The conventional organic EL element has a higher driving voltage than the inorganic light-emitting diode, and the light-emitting luminance or luminous efficiency is also low. Moreover, the deterioration of characteristics is also obvious and it is impossible to achieve practical use. Recently, organic EL elements have been slowly improved, but further high luminous efficiency and long life are required. For example, a technique of using a single ciprofi compound as an organic luminescent material has been disclosed (Patent Document 1). However, in this technique, for example, at a current density of 1 mA/cm2, only a luminance of 1,650 cd/m2 is obtained, and the efficiency is i ed/A, which is extremely low and is not practical. Further, a technique of using a single biguanide compound as an organic light-emitting material has been disclosed (Patent Document 2). However, in this technique, the efficiency is also about 1 to 3 cd/A, which is low, and is intended to be improved by practical use. On the other hand, there is proposed a long-life organic component in which a distyryl compound is used, and a long-lived organic light-emitting material such as a stilbene 153939.doc 201136910 rare earth amine is added thereto (Patent Document 3). However, the life of the element is not sufficient, and further improvement is sought. Further, there is no technique for using a mono- or a bis-indenyl compound and a distyryl compound as an organic light-emitting medium layer (Patent Document 4). However, in these techniques, due to the light-weight structure of the styryl compound, the luminescence spectrum is long-wavelength and the color purity is deteriorated. Further, Patent Document 5 discloses an invention in which an aromatic amine derivative having an extended aryl group and a di-p-hydrofuran ring bonded to a nitrogen atom is used as a hole transporting material. An aromatic amine derivative in which a benzopyrene ring, a dibenzothiophene ring, a benzofuran ring, a benzothiophene ring or the like is bonded to a nitrogen atom via an aryl group, and is used as a hole transporting material, but There is no example of use as a luminescent material. Further, Patent Document 7 describes the feeling of having a dibenzofuranylamino group. However, we hope to further improve luminous efficiency and longevity. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Patent Document No. 2001-284050 Patent Document 5: Japanese Patent No. 3508984 Patent Document 6: International Publication No. WO2007/125714 Patent Document 7: International Publication No. WO2009/084572A No. 153939.doc 201136910 [Invention] DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above problems, and an object thereof is to provide an organic EL device having a long life and high luminous efficiency and an amine-based fluorene derivative obtained therefrom. Technical means of solving problems

The present inventors have conducted active research in order to achieve the above object, and as a result, found that an amine group having a terminal substituent such as a dibenzofuran ring of a dibenzothiophene ring bonded at a position other than the two positions The derivative is used as a material for an organic EL, and has high luminous efficiency and long life, thereby completing the present invention. That is, the present invention provides an amine-based oxime derivative represented by the following formula (1). [In the formula, R represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a substituted or unsubstituted ring to form an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted ring. a heterocyclic group having 5 to 50 atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 5 carbon atoms, substituted or not Substituted carbon number (9), alkoxy group, substituted or unsubstituted ring, aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted ring, aryloxy group having 6 to 50 carbon atoms, A substituted or unsubstituted ring forms an arylthio group having a carbon number of 5 Å, a substituted or unsubstituted alkoxycarbonyl group having a carbon number of 2 to 5 Å, forgotten 153939.doc · 5_ 201136910 substituted or unsubstituted An aryl group and/or an alkyl decyl group, a carboxyl group, an amine group, a cyano group, a nitro group or a thio group. m is an integer of 1 to 8, and when m is 2 or more, 'a plurality of r' may be the same or different.

Ar-Ar4 is independently a substituted or unsubstituted ring to form an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted alkyl group having a carbon number of 〇~5〇, a substituted or unsubstituted ring. The cycloalkyl group having a carbon number of 3 to 50 is formed, the substituted or unsubstituted ring forms an aralkyl group of 7 to 50, or the substituted or unsubstituted ring forms a heterocyclic group having 5 to 50 atoms. Among them, one or more of Ar Guang An is a group represented by the following formula (2), (3) or (4). [Chemical 2]

(wherein X is oxygen (0), sulfur (S) or habitat (Se), the rule 2 is a hydrogen atom, a substituted or unsubstituted ring forms an aryl group having a carbon number of 6 to 60, substituted or not Substituted carbon number 1 to 5 0, a substituted or unsubstituted carbon number 2 to 5 稀 of a dilute group, an amine group, a substituted or unsubstituted carbon number of 50 alkoxy group, a substitution or The unsubstituted ring forms an aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted ring to form an arylthio group having 6 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms a carbonyl group, a halogen atom (preferably a fluorine atom), a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted aryl group and/or an alkyl decyl group or a slow group. η is an integer of 1 to 7' When η is 2 or more, a plurality of r's may be the same or different, and when R2 is plural, they may be bonded to each other to form a saturated or unsatisfactory substituted divalent group. There is no & key 153939.d〇c 201136910 in the case of the 5-member ring part of X)]. Further, the present invention provides an organic anal element which is between a cathode and an anode = an organic thin film layer containing a layer or a plurality of layers of a light-emitting layer and at least one layer of the organic thin film layer contains the above-described amine-based derivatization As a component of singly or as a mixture. EFFECT OF THE INVENTION The organic light-emitting efficiency of the organic anion device using the amino derivative of the present invention is difficult to deteriorate and has a long life even when used for a long period of time. [Embodiment] The anthracene derivative of the present invention is a compound represented by the following formula (1). Αγ4(1) Formula (1) X, Ri is a hydrogen atom 'halogen atom (preferably a fluorine atom), and the substituted j unsubstituted ring forms a carbon number of 6 to 50 (preferably, the ring forms a carbon number of 6~) 2〇) = a substituted or unsubstituted ring to form a heterocyclic group having 5 to 5 Å (preferably, V to 5 to 20), substituted or unsubstituted carbon number (preferably a slave number of 1 to 20), a substituted or unsubstituted cycloalkyl group having a carbon number of 35 Å (preferably a ring forming carbon number of 5 to 12), substituted or unsubstituted The alkoxy group having a carbon number of 1 to 5 Å (preferably having a carbon number of 1 to 20), substituted or unsubstituted, forms a carbon number of 7 to 5 Å (preferably, a ring-forming carbon number of 7 to 2 Å). The aralkyl alcohol, the substituted or unsubstituted ring forms an aryloxy group having a carbon number of 6 to 50 (preferably, the ring forms a carbon number of 7 to 20), and the substituted or unsubstituted ring forms a carbon number of 153,939. Doc 201136910 (preferably % formed carbon number 7~2〇) arylthio group substituted or not taken, inverse 5G (preferably carbon number 2~2Q) of the oxy group, substituted or not & substituted square group and / or calcification base, mercapto group, amine group, cyano group Shockey or & yl. „! is an integer of ~8 (preferably Bu 4, and further preferably Bu 2). When m is 2 or more, oh stick ugly > „ 士 ^ ^ On the If shape, the plurality of hearts can be the same, It can also be different. Hereinafter, specific examples of the respective groups indicated by R1 will be described. Examples of the above aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group 4-methylphenyl ' 4-ethylphenyl group, a biphenyl group, and a 4-methylbiphenyl group 4 -ethylbiphenyl, 4·cyclohexylbiphenyl, terphenyl, 3,dichlorophenyl, naphthyl, 5-methylcainyl, phenanthryl, anthracenyl, fenyl, thiol, propylene An olefinic group, a fluorenyl group, a 9,9-dimethyl fluorenyl group or the like. Examples of the heterocyclic group include imidazole, benzimidazole, pyrene, furan, thiophene, oxadiazoline, porphyrin, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrolazine, and imidazole. Residues of pyridine, piperidine, pyrimidine, benzofuran, dibenzofuran, stupid thiophene, dibenzothiophene, triple p well, and the like. Examples of the alkyl group include a linear or branched alkyl group having a carbon number of 2, and a linear or branched haloalkyl group having a carbon number of 1 to 20, and examples thereof include a methyl group, an ethyl group, a propyl group and a different form. Propyl, butyl, t-butyl 't-butyl, pentyl, hexyl, heptyl, octyl, stearyl, 2-phenylisopropyl, trimethylmethyl, difluorodecyl, benzyl , α-phenoxybenzyl, α,α-dimethylbenzyl, to _methylbenzyl benzyl, α,α-mono(difluoromethyl)benzyl, triphenylmethyl, heart Benzyloxybenzyl and the like. 153939.doc 201136910 Examples of the above cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an anthranyl group, a cyclooctyl group, a cyclodecylbicycloheptyl group, a bicyclooctyl group, and a tricyclic ring. The heptyl group, the adamantyl group and the like are preferably a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicycloheptyl group, a bicyclooctyl group or an adamantyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group, and various pentane groups. Oxyl group, various hexyloxy groups, and the like. Examples of the above aralkyl group include a benzyl group, a phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, and a phenyl tert-butyl 'α- Naphthylfluorenyl, 1-α-naphthylethyl, 2 (indolylethyl, 1α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylfluorenyl, naphthyl Base, 2_β-naphthylethyl, 1-β-naphthylisopropyl, 2β-naphthylisopropyl, 1α-pyrrolylmethyl, 2-(1-n-pyryl)ethyl, palladium Benzyl, m-decyl benzyl, o-decyl benzyl, p-chlorobenzyl, m-benzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-benzyl , m-benzyl, o-benzyl, p-benzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl , m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, b-hydroxy-2-phenylisopropyl, 1-oxa-2·phenyl Examples of the aryloxy group and the arylthio group are _〇γ and _SY, and γ is the same as the above-mentioned aryl group. The carbonyl group is represented by _C〇〇Z, and Z is the same as the above-mentioned alkyl group. Examples of the above aryl group and/or alkyl decyl group include trimethyl sulfonium 153939.doc 201136910, triethyl. a decyl group, a triphenyl decyl group, a tert-butyl dimethyl fluorenyl group, a tert-butyldiphenyl fluorenyl group, etc. In the formula (1), 'Αη-Αι*4 is independently substituted or not The substituted ring forms an aryl group having a carbon number of 6 to 50 (preferably, a ring forming carbon number of 6 to 2 Å), a substituted or unsubstituted carbon number of 1 to 50 (preferably, a carbon number of 1 to 20). The alkyl group, the substituted or unsubstituted ring forms a cycloalkyl group having a carbon number of 3 to 50 (preferably, a ring forming carbon number of 5 to 12), and a substituted or unsubstituted ring forms a carbon 7 to 5 Å (more) Preferably, the ring forms a aryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted ring forms a heterocyclic group having an atomic number of 5 to 50 (preferably, a ring forming atomic number of 5 to 2 Å). Specific examples of the respective groups represented by Αγ and Αγ4 are the same as the above-mentioned examples. The one or more of Ari to Ar·4 are represented by the following formula (2), (3) or (4). Based on 1st, 3rd, 4th In the intramolecular steric hindrance, an amine fluorene derivative having a rigid and sterically bulky terminal substituent such as a dibenzofuran ring or a dibenzo thiophene ring is used as a material for an organic EL device. In addition, it is considered that it is possible to prevent the intermolecular association, and it is considered that it becomes difficult to concentrate the light to have high luminous efficiency, and the life is prolonged.

In the formula (2) (4), X is oxygen (〇), sulfur (§) or sprinkled (Se), & is a hydrogen atom 'substituted or unsubstituted ring to form a carbon number of 6 to 60 (preferably The ring forms an aryl group having 6 to 2 Å of carbon, a substituted or unsubstituted carbon number 5G (preferably carbon number 153939.doc 201136910 1 to 20) alkyl group, substituted or unsubstituted carbon An alkoxy group having 2 to 5 Å (preferably a carbon number of 2 to 2 Å), an alkenyl group, an amine group, a substituted or unsubstituted carbon number of 1 to 50 (preferably a reciprocal number of 1 to 20) The substituted or unsubstituted ring forms an aryloxy group having a carbon number of 6 to 50 (preferably, a ring forming carbon number of 7 to 2 Å), and a substituted or unsubstituted ring forms a carbon number of 6 to 50 (preferably, An arylthio group having a carbon number of 7 to 2 Å), a substituted or unsubstituted alkoxycarbonyl group having a carbon number of 50 (preferably a carbon number of 2 to 2 Å), a halogen atom (preferably fluorine) Atom), cyano, nitro, hydroxy, substituted or unsubstituted aryl and/or alkylalkyl or carboxyl. η is an integer of 1 to 7 (preferably 1 to 4), and when 11 is 2 or more, the plural & may be the same or different. It is particularly preferable that the above x is (氧) in oxygen (〇), sulfur (s) or selenium (Se). Further, in the case of plural cases, they may be bonded to each other to form a saturated or unsaturated, substitutable divalent group. Also, there is no & keyed in the case of the $ member ring portion of X. And 'specific examples of the respective groups shown by R2 which are the same as the above-mentioned cores, and examples of the rare groups which are not present in the heart include, for example, an ethylene group, a dilute propyl group, a 1-butenyl group, and a 2- Butenyl, 3-butenyl, anthracene, 3-butadienyl, i-methylethylene, stupidyl, 2,2, diphenylvinyl, M•diphenylvinyl, and the like. In addition, as a case of the case where 乂 is oxygen and sulfur, for example, the following structures and the like are exemplified, but are not limited to the above-exemplified compounds. X, even if it is oxygen or sulfur, the same can be cited. 153939.doc 201136910 g^r In the above-mentioned formulas and the "substituted or unsubstituted bases" of the respective formulae described below, examples of the substituents include substitution or The unsubstituted % forms an aryl group having 6 to 50 Å, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 丨 咒 之 alkoxy group, substituted Or an unsubstituted ring to form an aralkyl group having 7 to 5 carbon atoms, a substituted or unsubstituted ring to form an aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted ring to form a carbon number of 6~ An alkoxycarbonyl group, an amine group, a functional atom (preferably a fluorine atom), a substituted or unsubstituted aryl group and/or an alkyl group of a 50-arylthio group, a substituted or unsubstituted carbon number. Based on alkyl, cyano, nitro, thiol, carboxyl, etc. 5 haizhuo 'better of the number of slaves 1 to 1 院, the number of carbons ~ 7 ring ' ' carbon number ι ~ ιο The alkoxy group is more preferably an alkyl group having a carbon number of 66 or a cycloalkyl group having a carbon number of 5 to 7, more preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a second group. Butyl, tert-butyl, positive "pentyl, n-hexyl, cyclopentyl, cyclohexyl. 153939.d〇c •12· 201136910" means "by aroma" "not only contains a monovalent aryl group" but also in the present invention "A base derived from the removal of a hydrogen atom in an aryl group contains a divalent "extension aryl group". The term "unsubstituted" means a hydrogen atom substitution. The hydrogen atom of the compound described in the present specification contains light hydrogen, and in the above formula (!), Ar and ΑΓ3 are preferably a group represented by the above formula (7), (7) or (4), and more preferably (4). ). The above formula (1) is preferably represented by the following formula (6). [Chem. 6] <β> (wherein ΑΓΐ~ΑΓ4 are the same as above, and R" and Ri2 are the same as r! respectively). Preferably, the 2-position of the exfoliation group of the formula (6) has a -hearted enthalpy and the 6-position is bonded with -NAr3Ar4' or the 9-position of the exciplex of the formula (6) has _νΑγ 】 2 and 10 positions are bonded with -NAr3Ar4. Specific examples of the amine hydrazine derivative represented by the formula (1) of the present invention are listed below, but are not limited to the exemplified compounds. [Chemistry 7]

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153939.doc -14- 201136910

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♦ _物鳞鲁 Dtp OUT MV DW w BI1>

I53939.doc -15- 201136910

Next, a method for producing the aminoguanidine derivative of the present invention will be described. The method for producing the aminoguanidine derivative represented by the formula (1) of the present invention is not particularly limited, and it may be produced by a known method. For example, Chem, Commun, 1997, 73 (MA Rabjohns et al.) may be used. The 2,6-dibromofluorene obtained by the method of the above I is aminated by a diarylamine to produce an aromatic amine derivative. 153939.doc -16-201136910 The amine-based anthracene derivative of the present invention is suitably used as a material for an organic EL element, and particularly preferably a light-emitting material' is suitably used as a blue light-emitting material or a green light-emitting material. Further, the aminoguanidine derivative of the present invention is also suitable as a doping material for an organic EL device. The organic EL device of the present invention is an element in which one or more layers of an organic thin film layer are formed between an anode and a cathode. In the case of a layer type, a light-emitting layer is provided between the anode and the cathode. The light-emitting layer contains a light-emitting material, and in addition, a hole injection material or an electron transport material may be contained in order to transport the hole injected from the anode or the electron injected from the cathode to the light-emitting material. The amine-based anthracene derivative of the invention has high luminescence property and has excellent hole injecting property, 'hole transmission property and electron injecting electron transport, which can be used as a luminescent material or a doping material. In the luminescent layer. In the organic EL device of the present invention, it is preferred that the light-emitting layer contains the amine-based fluorene derivative of the present invention in an amount of usually "% by weight, more preferably 1 to 10% by weight. Since the amine-based fluorene derivative has a very high fluorescence quantum efficiency, a high hole transporting ability, and an electron transporting ability, a uniform film can be formed, so that the luminescent layer can be formed only by the amine fluorene derivative. When the amine-based anthracene derivative of the present invention is used as a light-emitting material for an organic EL device, it is preferred that the light-emitting layer contains at least one of the amine-based anthracene derivatives of the present invention and is selected from the group consisting of the following formula (40). At least one of the compounds selected from the group consisting of the amine hydrazine derivatives of the present invention is preferably a push material; at least one of the compounds represented by the following formula (40) is preferably at least Main forgotten 153939.doc 17 201136910 Body material. Hereinafter, the compound represented by formula (40) will be described.

(In the formula (40), a hydrogen atom, a fluorine atom, a substituted or unsubstituted carbon number, an alkyl group, a substituted or unsubstituted cycloalkyl group having a carbon number of 3 to 1 Å, respectively. A substituted or unsubstituted alkyl decyl group having a carbon number of 3 to 3 Å, a substituted or unsubstituted ring, an aryl decyl group having a carbon number of 8 to 3 Å, a substituted or unsubstituted carbon number 丨~ The alkoxy group of (9), the substituted or unsubstituted ring forms an aryloxy group having 6 to 20 carbon atoms, the substituted or unsubstituted ring to form an aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted The ring forms a heterocyclic group of 5 to 3 Å, and 2、 2 indicates that the substituted or unsubstituted ring forms an aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring number 5 ~30 heterocyclyl). The formula (40) is preferably a group in which Ar12 and Ar13 are different. In the above formula (40), at least one of ruthenium and Aru is preferably a substituted condensed ring group having a substituted or unsubstituted ring to form an atomic number of 丨〇~3 过. The anthracene derivative represented by the formula (41). 153939.doc -18- 201136910 [Chem. 12]

(wherein, the Ar1G1 to A cores are each independently a substituted or unsubstituted ring to form an aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring to form a heterocyclic group having 5 to 30 atoms; ). The anthracene derivative represented by the above formula (41) is preferably an anthracene derivative represented by the following formula (42), (i) 3) or (44). [Chem. 13]

Rn and R32 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having a carbon number of 3 to 1 fluorene, substituted or unsubstituted. The alkyl decyl group having a carbon number of 3 to 30, the substituted or unsubstituted ring forming an aryl sulfonyl group having a carbon number of 8 to 30, a substituted or unsubstituted ring to form a carbon number of 6 to 30 The group or the substituted or unsubstituted ring forms a heterocyclic group having 5 to 30 atoms. a and b are each independently an integer from 1 to 7). In the above formula (42), when a is 2 or more, a plurality of r31 may be the same as 153939.doc 1 Ω 201136910, respectively, and may be different, and adjacent states may be in the form of (43) b and R32. same. Long people. This situation is for [Chem. 14]

Wherein ' Arm~Al*1Q5 are independently substituted or unsubstituted (4 4) groups, or substituted or unsubstituted rings form an atom VIII 4 丨 Κ 42 respectively independently substituted for hydrogenogen 4 or not Substituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 1 ring carbon number, substituted or unsubstituted alkyl decyl group having 3 to 3 carbon atoms, Taking an unsubstituted ring to form an aryl group having a carbon number of 8 to 3 G, a substituted or unsubstituted ring to form an aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring to form an atomic number of 5 to a heterocyclic group of 30. c and d are each independently an integer of ι to 4). In the formula (44), when c is 2 or more, the plurality of r4丨 may be the same or different, and the adjacent R41 may form a ring with each other. This is the same for d and R42. An 〇 3 of the above formulae (41), (42), (43) and (44) is preferably a substituted or unsubstituted phenyl group. Further, (40) is preferably a derivative of the following formula (48). Anthracene derivative (45) is an indole derivative represented by formula (40): R101, r102, 153939.doc • 20·201136910 R] 07, R108, mid-red red ^., either of which is substituted or not The substituted ring forms a carbon number 6 to = aryl group. The substituted or unsubstituted ring forms an atomic number. (1) The oxime group, the 'k' substituted or unsubstituted ring forms a carbon number 6~ Chuanzhifang Base, or. The substituted or unsubstituted ring forms a heterocyclic group having an atomic number of 5 to 3 Å, R, /102, R, 07, and R1°8, and R1.1, R1. 2, and Ri. Any one of R, R1〇R~6, which is represented by a hydrogen atom of the formula (4〇), is a substituted or unsubstituted ring forming a Wei 6~ aryl group, Or a substituted or unsubstituted ring to form a heterocyclic group having 5 to 3 atomic number; a substituted = substituted ring to form an aryl group having 6 to 3 carbon atoms, or substituted or not all of R to R It is a hydrogen atom. Onion derivative block good order (Μ) is derived [Chemistry 15]

(wherein, Ar丨〇丨~Ar丨03 and Ar丨丨0 are respectively cut by molybdenum, and are independently substituted for the substituted or uncaptured % to form an aryl group having a carbon number of 6 to 30, seven soils, and work substitution. ^ ^ Or a substituted or unsubstituted hydrazine having a heterocyclic group of 5 to 30. The above formula (40) is preferably an anthracene derivative represented by the following formula ( ). 153939.doc

S 201136910 [Chem. 16]

(wherein Rl〇1~Rl08, Ar13 are the same as formula (40). The substituted or unsubstituted ring forms an aryl group having 6 to 3 carbon atoms, a substituted or unsubstituted ring to form an atomic number of 5 a heterocyclic group of ～3〇, a substituted or unsubstituted carboxylic acid group, a substituted or unsubstituted ring, a cycloalkyl group having a carbon number of 3 〇, substituted or unsubstituted a substituted or unsubstituted aryl group and/or an alkyl decyl group, a cyano group, or a fluorine atom having a carbon number of 1 to decyl. The stomach b is an integer of 0 to 7. In the case of an integer of bg2 or more When there are a plurality of R 11 , they may be the same or different. Among the anthracene derivatives of the formula (50), a derivative represented by the following formula (51) is preferred.

(wherein R丨0丨~Ri〇«, R丨丨丨, b are the same as formula (5〇). Substituted or unsubstituted alkyl group having 1 to 1 ring carbon number, ring forming carbon number 3~1 Cycloalkylene, or by Xun

Ar14 is a substituted or unsubstituted ring which forms an aryl group having a carbon number of 6 to 3 fluorene, which is ring-shaped, substituted or unsubstituted or substituted or unsubstituted. 153939.doc -22-201136910 a heterocyclic group having an atomic number of 5 to 3 0) Further, as Ar 4, it is preferably a 9,9-dimethylidyl group, a 9 9-diindenyl-2-yl group, 9, 9-Dimethyl-3-yl, 9 9 dimethyl-4-yl, dibenzofuran-1-yl, dibenzofuran-2-yl, dibenzofuranyl, or dibenzo Furan-4-yl. Further, the anthracene derivative may be any one of the anthracene derivatives represented by the following formulas (52) to (58), in addition to the formula (5〇). [Chem. 18]

(wherein R101 to R108 are the same as those of the formula (5〇).

Ar and Ar16 respectively represent a hydrogen atom, a ring forming an aryl group having a carbon number of 6 to 3 fluorene or a substituted or unsubstituted ring to form a heterocyclic ring having an atomic number of 5 to 30, and Ar»5 may be bonded together with the bonded naphthalene ring. Form a ring). [Chem. 19] 153939.doc (in the formula .17

Substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted -23·201136910 ring formed into a cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted ring forming atomic number 5 ~30 heterocyclyl).

For example, Ar17 is preferably a dibenzofuranyl group, a dibenzofuranyl group, a dibenzofuran-3-yl group, or a dibenzofuran-4-yl group.

(wherein R^-R78 are each independently a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 10, a substituted or unsubstituted carbon number of 3 to fluorene, A substituted or unsubstituted alkylalkylene group having 3 to 3 carbon atoms, or a substituted or unsubstituted ring to form an arylalkylalkyl group having 8 to 30 carbon atoms. R" is a hydrogen atom, substituted or not Substituted carbon number (7) alkyl group, substituted or unsubstituted carbon number 3 to 1 ring cycloalkyl group, substituted or unsubstituted alkyl group alkyl group having 3 to 30 carbon atoms, substituted or The unsubstituted ring forms an arylalkylalkyl group having a carbon number of 8 to 30, a substituted or unsubstituted ring to form an aryl group having 6 to 3 carbon atoms, or a substituted or unsubstituted ring to form an atomic number of 5 a heterobasic group of 〜30. e is an integer of 1 to 4. ΑΓ6 is a substituted or unsubstituted ring to form an aryl group having 6 to 30 carbon atoms, or a ring substituted or unsubstituted ring to form an atomic number of 5 to 3 a heterocyclic group of hydrazine. ΑΓ7 is a substituted or unsubstituted ring to form a condensed aryl group having a carbon number of 10 to 20 or a substituted or unsubstituted ring to form a condensation of an atomic number of 9 to 20. 153939.doc -24- 201136910 cycloalkyl group). [Formula 21]

(wherein R101 to R108 are the same as equation (50).

Ar is a substituted or unsubstituted ring to form an aryl group having 6 to 3 carbon atoms, a substituted or unsubstituted carbon number of 10, a substituted or unsubstituted % to form a carbon number of 3 to 10 The cycloalkyl group or the substituted or unsubstituted ring forms a heterocyclic group having 5 to 50 atoms. Further, Aru may form a ring together with the benzene ring to which it is bonded.

Ar19 is a substituted or unsubstituted ring to form an aryl group having 6 to 3 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted ring to form a carbon number of 3~ A cycloalkyl group of 10 or a substituted or unsubstituted ring forms a heterocyclic group having 5 to 30 atoms. [化22]

(wherein R1G1 to R1G8 are the same as those of the formula (50). L is a single bond, a substituted or unsubstituted ring forms a aryl group having 6 to 5 Å or a substituted or unsubstituted ring of 2 valence. A heterocyclic group having an atomic number of 5 to 5 Å is formed. 153939.doc • 25- 201136910 ΑΓ is a substituted or unsubstituted ring forming an aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted ring forming atom. a heterocyclic group of 5 to 3 G. X is an oxygen atom, a sulfur atom, _NRl31 r13 3, (1), η 132 η (1), Κ, R / Knife represents the same group as H101 to R 08. R is substituted Or an unsubstituted ring to form an aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted ring, a heterocyclic group having 5 to 3 (1) atomic groups, a substituted or unsubstituted carbon 1 to 1 G. a substituted or unsubstituted ring to form a cycloalkyl group having a carbon number of 3 to 1 G, a substituted or unsubstituted carbon number of 20, a substituted or unsubstituted aryl group and/or a sulphur stone When m is an integer β of 〇~7, when the melon is an integer of 2 or more, a plurality of R121 may be the same or different. [Chem. 23]

(wherein R101 to R108 are the same as those of the formula (50).

Ar22 is a substituted or unsubstituted ring to form an aryl group having 6 to 3 carbon atoms or a substituted or unsubstituted ring to form a heterocyclic group having 5 to 3 atomic number. R201 is a substituted or unsubstituted ring which forms an aryl group having 6 to 3 carbon atoms, a substituted or unsubstituted ring, a heterocyclic group having 5 to 30 atomic groups, a substituted or unsubstituted carbon number of 1 ~1 〇 alkyl, substituted or unsubstituted ring to form a cycloalkyl group having a carbon number of 3 to 10, a substituted or unsubstituted carbon number of 丨~2〇. 153939.doc -26- 201136910 The substituted or unsubstituted aryl group and/or alkylalkylalkyl 'cyano group, or fluorine atom, P is an integer of 0 to 4. In the case where p is an integer of 2 or more, a plurality of R201 may be the same or different). In addition to the above, a compound represented by the following formula (58) can also be suitably used as a host material.

(S8) In the organic EL device of the present invention, the formation of each organic layer such as a light-emitting layer can be carried out by using a true distillate or a molecular beam evaporation method (MBE method, molecular beam [e.g. 24] epitaxy), sputtering, plasma, A dry film forming method such as ion plating or a coating method such as spin coating, dipping, casting, bar coating, roll coating, shower coating, or ink jetting of a solution dissolved in a solvent. In particular, when the organic EL device is produced by using the aminoguanidine derivative of the present invention, the organic compound layer and the light-emitting layer can be formed not only by vapor deposition but also by wet film formation. The film thickness of each layer of the organic compound layer is not particularly limited, but it is necessary to set the film thickness of the field. Usually, if the film thickness is too thin, pinholes and the like are generated, and even if an electric field is applied, sufficient light-emitting luminance cannot be obtained. On the other hand, if it is too thick, a high applied voltage is required in order to obtain a constant light output, and the efficiency is changed.

S 153939.doc 27- 201136910 Poor, so usually the film thickness is estimated to be in the range of ~0.2μιη. In the case of the range of S'" ", and more preferably in the case of the wet film formation method, the organic-containing ELH material containing the amine-based hydrazine derivative of the present invention and a bathing agent can be used. The solution containing the solution as the organic component is preferably an organic EL containing at least one of the amines of the present invention and at least one selected from the compounds represented by the formulae (5〇) to (59). A solution of the material. In the case of (4), a solution containing an anal material is prepared by dissolving or dispersing the hunger material forming the respective layers in an accommodating agent to form a film, and the solvent is used as a solvent, for example, dichloro Methane, dichloro =, chloroform, carbon tetrachloride, tetrachloroethylene, trichloroethylene, chlorobenzene, two: chloroform, trifluoromethyl, and other halogen hydrocarbon solvents, or dibutyl ether, four Hydrogen tridentate, tetrahydro (tetra), second burner, benzal, dimethoxyethane, and other scaly solvents 'methanol or ethanol, propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol 'Methyl cellosolve, ethyl cellosolve, alcohol solvent such as ethylene glycol' acetone, methyl ethyl ketone, diethyl group, 2_hex嗣, methyl isobutyl ketone, 2 ng net, 4 · 嗣 嗣, —S τ τ * $fi — degree isobutyl ketone, acetonyl acetone, isophor _, cyclohexanone, methyl _, phenylethyl copper and other hydrazine solvents, benzene, toluene, sputum, ethyl benzene, hexane, cyclohexanthine, xinyuan, simmering, tetrachlorene, etc. (4) solvent 'acetic acid vinegar, butyl acetate, A vinegar solvent such as acetonitrile acetate, a chain carbonate acetal solvent such as diacetic acid carbonate, methyl acetonate or diethyl carbonate; a cyclic carbonate solvent such as ethylene carbonate or propylene carbonate; Further, it is preferably a hydrocarbon solvent such as toluene or dioxane or an ether solvent. Further, these solvents may be used singly or in combination of two or more. 153939.doc •28·201136910 In addition, in the 'any-organic compound layer, an appropriate resin or an additive may be added in order to improve film formability, prevent pinholes of the film, etc. As a usable tree, we can cite. Phenylacetone, polycarbonate, polyaryl vinegar, polyacetic acid, polyamine, polyurethane vinegar, poly stone, polymethyl ketone Insulating resin such as methyl vinegar, polyacetic acid methyl vinegar or cellulose, and copolymers thereof, etc., poly-*vinyl-salt, photosynthetic resin such as polyglycol, polyaniline, polybenzazole, polypyro Further, as the additive, an antioxidant, an ultraviolet absorber, a plasticizer, etc. may be mentioned. In order to improve the stability of temperature, humidity, ambient gas, etc. of the organic component obtained by the present invention, A protective layer may be provided on the surface of the element, or the entire protective element may be formed by using an oil or a resin. In the organic EL device of the present invention, it is preferable that at least one surface of the pair of electrodes is provided with a layer selected from a chalcogen compound and a toothed metal. (Layer of the organic EL element) The structure of the organic EL element of the present invention will be described below. The representative element configuration of the organic element of the present invention is exemplified ( 1) Anode / luminescent layer / cathode (2) Anode / hole injection layer / luminescent layer / cathode (3) Anode / luminescent layer / electron transport layer / cathode (4) Anode / hole injection layer / luminescent layer / electron transport Layer/cathode (5) yang Pole/Organic Semiconductor Layer/Light Emitting Layer/Cathode (6) Anode/Organic Semiconductor Layer/Electronic Barrier Layer/Light Emitting Layer/Cathode 153939.doc -29·201136910 (7) Anode/Organic Semiconductor Layer/Light Emitting Layer/Adhesion Improvement Layer/ Cathode (8) Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode (9) Anode / Insulation / Light Emitting / Insulating Layer / Cathode (10) % Pole / Inorganic Semiconductor Layer / Insulation Layer / luminescent layer / insulating layer / cathode (11) anode / organic semiconductor layer / insulating layer / luminescent layer Λ insulating layer / cathode (12) anode / insulating layer / hole injection layer / hole transmission layer / luminescent layer / insulation Layer/cathode (13) Anode/insulating layer/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode and the like are generally preferably used. The organic EL device of the present invention is fabricated on a light-transmissive substrate. The light-transmitting substrate as used herein supports a substrate of an organic EL element, and preferably has a light transmittance of a viewing area of 400 to 700 nm and a smooth transmittance of 5% or more. Specifically, a glass plate, a polymer plate, etc. can be mentioned as a glass plate, and a sodium-lime-glass glass, a glass containing a 钡'锶, a lead glass, an aluminum octanoic acid glass, a borosilicate glass, and a bismuth borosilicate glass are mentioned. , quartz, etc. Further, examples of the polymer sheet may include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfone, and polysulfone. The anode of the organic EL device of the present invention is responsible for injecting a hole into the hole transport layer or the light-emitting layer, and has an effect of having a work function of 4.5 ev or more. Specific examples of the anode material used in the present invention include emulsified indium tin oxide (ITO, Indium Tin Oxide), tin oxide (NESA, Nesse), gold, silver, platinum, copper, and the like. Further, as the anode, for the purpose of injecting electrons into the electron transport layer or the light-emitting layer, 153939.doc • 30·201136910 is preferably a material having a small power. The anode can be produced by forming the electrode material into a thin film by a vapor deposition method or a sputtering method. v When the luminescence from the luminescent layer is thus taken out from the anode, it is preferred that the anode has a transmittance of illuminance of more than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω / □ or less. The film thickness of the anode is also dependent on the material, but is usually selected from the range of 10 nm to 1 μm, preferably 1 to 2 nm. The luminescent layer of the organic EL element has the following functions. That is to say: (1) Injection function: injection of electricity/same from the anode or the hole injection layer when the electric field is applied, and injection of electrons from the cathode or electron transport layer) (7) Transmission function: the electric field can be injected The charge (the function of electron and electricity movement; (3) the function of the light-emitting function. Provide the place where the electron and the electric society are combined to make the light shine with it; the owner's ease and the ease of the electron can exist. The ability of the hole and the mobility of the electron to express the wheel can also exist 'but it is better to move the charge of either side. = The method of forming the luminescent layer, for example, the method of using the smelting method or the spin coating is a molecular deposition film. The method of knowing the law. The luminescent layer, especially the so-called molecular deposition film, refers to a film formed by deposition, or a film formed by solidification of a solution-like material or a compound of a material, usually a stack of material assemblages of the molecular pile. The film can be distinguished from the film formed by the £β method (molecular accumulation film) according to the difference in the structure of the agglomerate, the higher order structure, or the functional difference caused by the agglomeration. Further, after a binder such as a resin and a material compound are dissolved in a solvent to prepare a solution, the layer may be formed by a spin coating method to form a light-emitting layer. In the case where the amine-based tomb derivative of the present invention is used for the light-emitting layer, the amine derivative of the present invention can be used for any of the dopant material and the host material, which is particularly preferably used as a dopant material. Further, in the present invention, other known luminescence other than the luminescent material containing the amine hydrazine derivative of the present invention and the compound containing a condensed ring may be contained in the light-emitting layer as needed within the range not impairing the object of the present invention. Further, a light-emitting layer containing the other known light-emitting material may be laminated on the light-emitting layer containing the light-emitting material of the present invention. 50 nm, more preferably 7 to 5 〇 nm, ‘there is a light-emitting layer formed to be trapped ’. If it exceeds 50 nm, the thickness of the light-emitting layer is preferably 5 to 10 nm. If it is less than 5 nm, it is difficult, and the adjustment of the chromaticity becomes difficult. Hole injection. The transport layer helps to inject holes into the light-emitting layer: : Transmit to: Layer of the light region' The hole mobility is large, and the ionization energy can be below. As such a hole injecting and transporting layer, it is preferable that the electric field strength transmits the hole to the material of the light-emitting layer, and the degree of the electric field of, for example, 104 to 106 is preferably shifted by "cm2/V·sec." The right is at least 10· As a specific example, the substance and the tris-salt derivative may be exemplified by an arylamine derivative 1 group W-derived, a di-salt derivative, a street organism, a polyaryl 153939.doc • 32·201136910 hydrocarbon Derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, amine-substituted chalcone derivatives, carbazole derivatives, styrylpurine derivatives, anthrone derivatives, An anthracene derivative, a stilbene derivative, a decazane derivative, a polydecane system, an aniline copolymer or the like. Further, for example, 4 4,_bis(N-(1-naphthyl)-N-phenylamino)biphenyl (hereinafter abbreviated as NpD) having two condensed aromatic rings in the molecule, and 3 examples thereof The triphenylamine unit is bonded to a starburst type of 4,4,4,_3 (n-(4〇-methylphenyl)N-n-amino)dibenylamine (hereinafter abbreviated as mtd) and the like. Further, in addition to the aromatic dimethylene-based compound exemplified as the material of the light-emitting layer, an inorganic compound such as p-type Si or p-type Sic may be used as the material of the hole injection layer. The hole injection/transport layer may be used. The compound is formed into a thin film by a known method such as a vacuum deposition method, a spin coating method, or a tungsten-plating method, the LB method, and the film thickness is not particularly limited. The organic electroluminescent device of 5 nm to 5 μηι 毛 毛 夹持 夹持 夹持 夹持 夹持 夹持 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机At least one of the base-based derivatives and at least one selected from the compounds represented by the above formula (50), and the hole transport layer and The electric hole injection layer contains at least one organic electroluminescent device selected from the group consisting of an aryl (tetra) or an aryl 14 derivative.

The S electron transport layer is capable of injecting a layer of electrons into the light-emitting layer, and the electron mobility is large, which may be a layer or a plurality of layers β χ , and the adhesion improving layer is contained in the electron transport layer and contains a particularly good adhesion to the cathode. The layer of material. As a metal complex used in the electron transfer layer of I53939.doc •33- 201136910. The material, preferably 8-hydroxyquinoline or a derivative thereof, as a specific metal complex of the above 8-hydroxyquinoline or a derivative thereof, may contain oxin (usually 8-quinoline) A metal chelate compound of octagonal ketone of 8 or hydroxyquinoline, 8 hydroxyquinolinone. For example, Alq described in the item of the luminescent material can be used as the electron transport layer. In another aspect, the electron-transporting compound represented by the following formula is exemplified as the No. 17 diazole derivative. [Chem. 25]

(wherein Ar201, Ar202, Ar203, Ar205, Ar206 and Ar209 represent an aryl group which is substituted or not lightly substituted, and may be the same or different from each other.

Ar2°4, Ar207 and Ar208 represent a substituted or unsubstituted extended aryl group which may be the same or different). The electron transporting compound is preferably a film former. As the electron transporting material, those represented by the following formulas can also be used. [Chem. 26]

-34- 153939.doc S 201136910 (In the formulae (A) and (B), A1 to A3 are each independently a nitrogen atom or a carbon atom.

Ar3G1 is a substituted or unsubstituted ring to form an aryl group having 6 to 6 carbon atoms, or a substituted or unsubstituted ring to form a heterocyclic group having 5 to 6 atomic number, and ^3〇2 is a hydrogen atom, The substituted or unsubstituted ring forms an aryl group having 6 to 6 carbon atoms, a substituted or unsubstituted ring, a heterocyclic group having 5 to 6 atomic number, a substituted or unsubstituted carbon number 1~ An alkyl group of 20, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or such a divalent group. Wherein, and any of the oxime is a substituted or unsubstituted ring to form a condensed cyclic group having a carbon number of 1 〇 to 60, or a substituted or unsubstituted ring to form a single heterocondensation having an atomic number of 5 to 6 〇 Ring base. L", L12 and L13 are independently a single bond, a substituted or unsubstituted ring to form a aryl group having a carbon number of 6 to 6 G, a substituted or unsubstituted ring, and a hetero atomic group having an atomic number of 5 to 60. a base, or a substituted or unsubstituted extension. R is a halogen atom, a substituted or unsubstituted ring forms an aryl group having 6 to 6 carbon atoms, and a reduced or unsubstituted ring forms a heterocyclic group having 5 to 6 G atoms, substituted or unsubstituted. a condensed group having a carbon number of 1 (7), or an alkyl group having a substituted or unsubstituted carbon number of 20, an integer of which, when t_2 or more, 'a plurality of R's may be the same or different, and a plurality of adjacent groups may be adjacent to each other. It can be bonded to form a carbocyclic aliphatic ring or a carbocyclic aromatic ring. R31. A hydrogen, a substituted or unsubstituted ring to form an aryl group having 6 to 6 carbon atoms, a substituted or unsubstituted ring to form a heteroaryl group having an atomic number of 3 to 60, 153939.doc • 35·201136910 a nitrogen-containing heterocyclic derivative represented by a substituted or unsubstituted carbon number 2G or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or -Lu-Ar3G丨-Ar3G2) . HAr-L14-Ar401-Ar402 (wherein, HAr is a nitrogen-containing heterocyclic ring having 3 to 4 carbon atoms which may have a substituent, and is a single bond, and a ring having a substituent may form a carbon number of 6 to 6 Å. An aryl group, a ring which may have a substituent, a heterocyclic aryl group having an atomic number of 5 to 6 G or a fluorenyl group which may have a substituent 'Ar40' is a ring which may have a substituent to form a carbon number stone (2) The group, Ar(10) is a nitrogen-containing heterocyclic derivative represented by a ring which may have a substituent to form an aryl group having 6 to 6 carbon atoms or a ring having a substituent to form a heterocyclic group having 5 to 6 atoms. The organic electroluminescent device of the present invention is characterized in that an organic thin film layer containing at least one layer or a plurality of layers of a light-emitting layer is held between a pair of electrodes, and preferably the light-emitting layer contains at least i of the amine-based anthracene derivative of the present invention. And at least 1# selected from the compounds represented by the above formula (10), and the electron # transport layer contains at least an electroluminescent device of the compound represented by the formula (4), the formula (B) or the formula (C). Among the organic electroluminescent elements sandwiching an organic thin film layer comprising at least one of a plurality of layers of the luminescent layer, The layer contains at least one of the amine group f, the derivative of the present invention and at least one selected from the compounds represented by the above formula (9), and the hole transport layer and/or the same layer of the main layer contains a derivative selected from the group consisting of arylamines. The organic electroluminescent device of at least one of the compounds represented by the above formula (4), formula (B) or formula (c) is contained in the substance or the core (4) organism. The electron transport layer contains at least one of the compounds represented by the above formula (4), formula (B) or formula (c). I53939.doc -36 In addition, the nitrogen-containing heterocyclic derivative represented by the following formula (πι) and the following formula (ιν) can also be used in the organic EL device of the present invention.

Am R30, R302, R..., R·, ruthenium and r3〇6 in the formula (III) represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, substituted or not Any of the substituted aryl, substituted or unsubstituted heterocyclic groups. Wherein, R3 (n, R302, R303, R3〇4, r305 & r3〇6 may be the same 'may be different. R30丨 and R302, R303 and R3〇4 'r30, r306 or R training and R taking, R With ruler, ruler (10) and... "can form a condensed ring. One [28]

In the formula (r3m to R in n〇 is a substituent, preferably an electron attracting group such as a cyano group, an exact group, an anthracenyl group, a carbonyl group, a trifluoromethyl group or a halogen group. The organic electroluminescent device of the present invention is a system. Between the pair of electrodes, an organic thin film layer comprising a layer or a plurality of layers having a light-emitting layer is sandwiched, preferably the light-emitting layer contains at least one kind of the amine-based E derivative of the present invention and is selected from the above formula (10) At least the old compound, the hole transport layer and/or electricity 153939.doc

S 37· 201136910 The hole injection layer contains at least one selected from the group consisting of an arylamine derivative or an aryl carbazole derivative, and the electron transport layer contains the above formula (4), formula (B) or formula (at least 丨 of the compound represented by 〇2) And an organic electro-active material containing an organic compound layer of at least one of the compounds represented by the above formula (IV). ^ ^ Further, an inorganic compound such as p-type Si or p-type SiC may be used as a hole. The material of the injection layer. In a preferred embodiment of the organic EL device of the present invention, there is an element containing a reducing dopant in a region where electrons are transported or an interface region between a cathode and an organic layer. Here, a reducing dopant, It is defined as a substance that can reduce electron-transferring characters. Therefore, as long as it has a certain degree of reduction, various materials can be used, for example, an alkali metal such as Na, K, Rb, and Cs can be suitably used. Alkaline earth metal (Ca, Sr, Ba), rare earth metal, alkali metal oxide, alkali metal complex, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide or rare earth metal halide, alkali At least one of the group consisting of an organic complex of a metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. It is especially preferred that the work function is 2.9 eV or less. The reduction ability of the alkali metal such as the side is particularly high, and the addition of a small amount in the electron in-phase can improve the luminance of the organic EL element or extend the life. Further, as a reducing dopant having a work function of 29 ev or less, a combination of two or more kinds of alkali metals is also preferable. In the present invention, an electron transport layer made of an insulator or a semiconductor may be further provided between the cathode and the organic layer. In this case, the leakage of the current can be effectively prevented, and the electron injection can be used as the insulator. It is preferable to use the 153939.doc •38·201136910 to select the metal chalcogenide (for example, Li2〇, Κ2〇, Nad, Na2Se). Na2〇), soil test metal chalcogenides (such as Qo, Ba〇, SrO, BeO, BaS, CaSe), alkali metal compounds (such as uf, NaF, KF, LiC1, KC1, Na(3) and soil test_μ ( At least one metal compound of the group consisting of CaF2, BaF2, SrF2, MgF2, and BeF2). Further, as the semiconductor constituting the electron transport layer, β&

Ca, Sr, Yb, A Bu Ga, In, Li, Na, Cd, Mg, Si, Ta,

Any one or a combination of two or more kinds of oxides, nitrides, or oxynitrides of at least the old elements of Sb and Zn. Further, the inorganic compound constituting the electron transport layer is preferably a microcrystalline or amorphous insulating film. When the electron transport layer is composed of such an insulating film, a more homogeneous film is formed, so that it is possible to reduce pixel defects such as dark spots. As such an inorganic compound, the above-mentioned alkali metal chalcogen compound, alkaline earth metal sulfur can be mentioned. It is a compound, a tooth of an alkali metal, and a tooth of an alkaline earth metal. As the cathode, in order to inject electrons into the electron transport layer or the light-emitting layer, a metal having a small work function (4 eV or less), an alloy, a conductive compound, and a mixture thereof are used as the electrode material. Examples of such an electrode material include sodium, nano-unloaded alloy, town, lithium, silver alloy, lanthanum/alumina, aluminum-lithium alloy, indium, rare earth metal, and the like. The cathode can be produced by forming the electrode material into a thin film by a method such as vapor deposition or sputtering. In the case where the light from the luminescent layer is taken out from the cathode, it is preferred that the cathode has a transmittance of illuminance of more than 1%. 153939.doc -39· 201136910 In addition, the sheet resistance of the cathode is preferably several hundred Ω/□ or less, and the film thickness is usually 10 nm to 1 μm, preferably 5 〇 to 2 〇〇 nm. Since the organic EL element applies an electric field to the ultrathin film, pixel defects caused by leakage or short circuit are liable to occur. In order to prevent this defect, it is preferable to insert an insulating thin film layer between the electrodes. Examples of the material used in the insulating layer include oxonium, vaporized lithium, lithium oxide, fluorinated planer, cerium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, and aluminum nitride. Cerium oxide, cerium oxide, cerium nitride, boron nitride, molybdenum oxide, cerium oxide, vanadium oxide, and the like. Mixtures or laminates of these may also be used. By using the materials and the formation methods exemplified above, an anode, a light-emitting layer, a hole injection layer as needed, and an electron transport layer as needed are formed to form a cathode, whereby an organic EL element can be produced. Further, an organic element may be fabricated in the reverse order from the cathode to the anode. In the following, an example of production of an organic EL device having a structure in which an anode/hole injection layer/light-emitting layer/electron transport layer/cathode is provided in order on a light-transmitting substrate is described. First, a film containing an anode material is formed on a suitable light-transmitting substrate by vapor deposition or sputtering. An anode is formed by a film thickness of a range of μm or less, preferably in the range of . A hole injection layer is then provided on the anode. The formation of the hole injection layer can be carried out by a vacuum deposition method, a spin coating method, a casting method, or an LB method as described above, but it is preferable to obtain a homogeneous film and to easily form pinholes. It is formed by using a vacuum distillation method. In the case of forming a hole injection layer by vacuum evaporation, it is vaporized 153939.doc 201136910 plating conditions depending on the compound used (material of the hole injection layer), the crystal structure of the target hole injection layer or recombination The structure is different, but it is usually preferably at a vapor deposition source temperature of 5 〇 to 45 (rc, vacuum degree ι〇_7 to ι〇_3 T〇rr, and a plating rate of 0.01 to 5 〇 nm/sec, The substrate temperature is preferably selected within a range of 5 〇 to 3 〇 (rc, film thickness 5 nm to 5 μηι.), the formation of the light-emitting layer on the hole injection layer can also be performed by using the desired organic light-emitting layer. The material is formed by thinning an organic light-emitting material by a vacuum vapor deposition method, a reduced ore method, a spin coating method, a washing method, or the like, and it is easy to obtain a homogeneous film and it is difficult to generate pinholes. It is formed by a vacuum evaporation method. In the case of using a vacuum deposition method: a light-emitting layer, the vapor deposition conditions vary depending on the compound used, but can usually be selected from the same range of conditions as the hole injection layer. Then, an electron is placed on the luminescent layer The transport layer, which is formed by the vacuum evaporation method, is preferably formed by a vacuum evaporation method because it is necessary to obtain a homogeneous film. The evaporation conditions can be selected from the same range of conditions as the hole injection layer and the light-emitting layer. When the compound of the present invention is used in the vacuum evaporation method, it may be co-deposited with other materials. Further, in the case of using the spin coating method, it may be contained by mixing with other materials. The organic EL device is obtained by laminating the cathode. The cathode is made of metal, and the vapor deposition method or the sputtering method can be used. However, in order to protect the organic layer of the substrate from damage during film formation, a vacuum evaporation method is preferred. The organic EL device described so far is preferably produced by continuously vacuuming from the anode to the cathode by vacuuming at 153939.doc -41 - 201136910. The film thickness of each organic layer of the organic EL device of the present invention is There is no particular limitation. Usually, if the film thickness is too thin, defects such as pinholes are likely to occur. On the other hand, if the film thickness is too thick, a high applied voltage is required, and the efficiency is deteriorated. Therefore, it is usually preferably in the range of several nm to 1 μm. When a DC voltage is applied to the organic EL element, when a voltage of 5 to 4 〇 ν is applied with the anode as the + and the cathode as the _, the luminescence can be observed. Even if the voltage is applied in the opposite polarity. The current does not flow, and no light is generated at all. Further, when an alternating voltage is applied, uniform light emission is observed only when the anode becomes + and the cathode becomes _. The waveform of the applied alternating current can be arbitrary. The organic EL element can be used for a light source such as a flat panel display such as a flat panel display for a wall-mounted television, a photocopying machine, a printer, a backlight of a liquid crystal display, a light source, a display panel, an identification lamp, etc. Further, the material of the present invention can be used not only In the organic EL device, it can also be used in the fields of electronic photoreceptors, photoelectric conversion devices, solar cells, image sensors, and the like. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, and the present invention is not limited to the following examples, unless otherwise construed. Synthesis Example 1 (Synthesis of Compound D16) was synthesized by the following procedure. [化29]

(Synthesis Example A) 153939.doc

-42· 201136910

Toluene

(Synthesis Example B) <0

NtPHtOf shouting

(Synthesis Example C) (Synthesis Example D) (1) Synthesis of Intermediate (b) (Synthesis Example A) In a 300 mL eggplant-shaped flask, an intermediate (a), 10.7 of 丨i 7 g was added under a stream of argon gas. 5% of aniline, hydrazine·63 g of tris(dibenzylideneacetone)dipalladium(0)[Pd2(dba)3], 0.87 g of 2,2,-bis(diphenylphosphinobiphthalene [BINAP] 9.1 g of the second butanol and 131 mL of dehydrated benzene were reacted at 85 ° C for 6 hours. After cooling, the reaction solution was filtered through diatomaceous earth, and the obtained crude product was subjected to gel chromatography (positive The alkane/dichloromethane (3/1) was purified, and the obtained solid was dried under reduced pressure to give a white solid of 1 〇g, which was analyzed by Fd_MS (Field Desorption Mass Spectrometry). , identified as the intermediate (b). (2) Synthesis of the intermediate (c) (Synthesis Example b) 153939.doc -43- 201136910 Add to the 500 mL flask in argon "it. 16 g intermediate

(b), 10 g of 2,6-dibromoindole, 5.5 g of sodium t-butoxide, 31 mg of acetic acid, l6(II) [Pd(OAc)2], 280 mg of three-third Butylphosphine, dehydrated benzene of wo mL was reacted for 7 hours while refluxing toluene. After cooling, 'methanol was added to the reaction solution, and the crude product obtained by filtration was purified by silica gel chromatography (toluene), and the obtained solid was recrystallized from toluene to dryness under reduced pressure to obtain a darkness of i 3 g. Red solid. It was identified as intermediate (c) by analysis of FD-MS. (3) Synthesis of intermediate (d) (Synthesis example) Under a stream of argon, add 4 〇g of intermediate (c), 100 mL of dehydrated THF to a 300 mL flask, and cool to _65. After °C, 18 mL of n-butyllithium hexane solution (1·57 M) was added and the reaction was carried out for a few hours. At the same temperature, 65 g of 4-bromodiphenyl group was added, and after 2 hours of reaction, the temperature was gradually raised. The mixture was reacted for 3 hours at room temperature. After adding a saturated aqueous solution of ammonium chloride to the reaction solution and separating the layers, the organic layer was washed with saturated brine and dried over magnesium sulfate. Purification with ethyl acetate/hexanes, and dried under reduced pressure to give 5,9 g of brown solids, which was identified as intermediate (4) by FD-MS analysis. (4) Synthesis of compound D16 (synthesis example) to 300 Add 5.9 g of intermediate (d), 24 g of potassium iodide, 760 mg of sodium phosphonate monohydrate, and i〇〇mL of acetic acid to an eggplant-shaped flask of mL, and react for 6 and a half hours under reflux of acetic acid. After cooling, adding sterol to the reaction solution will filter the crude product obtained.

I53939.doc -44 - S 201136910 was purified by silica gel chromatography (ethyl acetate / toluene / hexane). The solid obtained was washed with dioxane and toluene and dried under reduced pressure to give 1.1 g. Yellowish white solid. It was identified as Compound D16 by FD-MS analysis. Synthesis Example 2 (Synthesis of Compound D26) was synthesized by the following procedure. [化30]

In the synthesis of the intermediate (c) of Synthesis Example 1, the synthesis was carried out in the same manner except that the intermediate (e) was used instead of 2,6-dibromofluorene. It was identified as Compound D26 by analysis of FD-MS. Synthesis Example 3 (synthesis of compound D41) was synthesized by the following procedure. [化31]

S was synthesized in the same manner as in the synthesis example A of Synthesis Example 1, except that the intermediate (1) was used instead of the intermediate (a). It was identified as an intermediate (g) by FD-MS analysis. 153939.doc -45- 201136910 In Synthesis Example B, the synthesis was carried out in the same manner except that the intermediate (g) was used instead of the intermediate (b). It was identified as an intermediate (8) by analysis by FD-MS. In the same manner as in the synthesis example C, the intermediate (h) was used instead of the intermediate (c), and the bromobenzene was used instead of the 4-bromodiphenyl group. Dream Analysis by FD-MS · 'identified as an intermediate (丨). In the synthesis of Example D, except that the intermediate (1) was used instead of the intermediate (d), it was synthesized in the same manner. It was identified as D41 by analysis of FD-MS. Synthesis Example 4 (synthesis of compound D71) was synthesized by the following procedure. [化32]

In Synthesis Example 2, the intermediate (g) was used instead of the intermediate (b), and the intermediate (1) was used instead of the intermediate (e), and the same procedure was used. It was identified as D71 by analysis of FD_MS. Synthesis Example 5 (synthesis of compound D81) was synthesized by the following procedure. [化33]

153939.doc -46 - S 201136910

In Synthesis Example A of Synthesis Example 1, the synthesis was carried out in the same manner except that the intermediate (k) was used instead of the intermediate (a). It was identified as the intermediate (1) by FD-MS analysis. In Synthesis Example B, the synthesis was carried out in the same manner except that the intermediate (1) was used instead of the intermediate (b). By FD-MS analysis, it was identified as an intermediate (m) in Synthesis C, except that instead of the intermediate (c), an intermediate was used, and instead of 4-bromodiphenyl, bromobenzene was used instead. The method was synthesized and identified as the intermediate (n) by FD-MS analysis. In the synthesis example D, except that the intermediate was used instead of the intermediate (d), it was synthesized by the same method, by FD-MS. Analysis, identified as D81. Synthesis of solid addition* Example 6 (synthesis of compound D116) was synthesized by the following procedure.

In Synthesis Example 2, except that the intermediate (1)' was used instead of the intermediate (1), and the intermediate (c) was used instead of the intermediate (c), the same was used.

S 153939.doc -47- 201136910 Method synthesis. It was identified as 0116 by analysis of FD-MS. Example 1 A transparent electrode comprising indium tin oxide was provided on a glass substrate of 25 x 75 x 0.7 mm size with a film thickness of 13 Å. After the glass substrate was irradiated with ultraviolet rays and ozone, the substrate was placed in a vacuum vapor deposition apparatus. First, Ni, N"-bis[4-(diphenylamino)phenyl]-^, _diphenyl phenyl-4,4'-diamine was evaporated to a thickness of 60 nm. As a hole injection layer, N, N, N, N, -4 (4-linked styrene)_4,4,•benzidine is evaporated thereon to a thickness of 2 〇 nm as a hole transport layer. . Then, 9_(2_nyl)-10-[4-(1-naphthyl)phenyl]oxime as a host material and the above-mentioned compound 〇16 as a dopant material are simultaneously vapor-deposited at a weight ratio of 40:2 to form A light-emitting layer having a thickness of 4 〇 nm. Then, tris(8-hydroxyquinolinyl)aluminum was vapor-deposited to a thickness of 2 Å to serve as an electron transport layer. Then, lithium fluoride was evaporated to a thickness of 丨nm, and then aluminum was evaporated to a thickness of 1 to 50 nm. This aluminum/lithium fluoride functions as a cathode. Thus, an organic EL element was produced. The obtained component was subjected to an energization test, and as a result, a blue light emission having a luminous efficiency of 19 3 Cd/A and a luminance of 193 〇cd/m 2 was obtained at a voltage of 5 9 v and a current density of 10 mA/cm 2 (luminous maximum wavelength: 5 〇 9 nm) ). A continuous DC current test was conducted at an initial luminance of 3000 cd/m2, and the half life was 4,000 hours. Example 2 In Example 1, an organic EL device was produced in the same manner except that Compound D26 was used as a dopant material instead of Compound D丨6. 153939.doc 48

S 201136910 The obtained component was subjected to a power-on test, and as a result, a blue light emission (luminous maximum wavelength: 499 nm) of a luminous efficiency of 18.0 cd/A and a luminous luminance of 2 was obtained with a voltage “v, a current density of 1 〇 mA/cm 2 . The initial decay test result of the initial luminance of 3000 ed/m was DC, and the half-life was 3,500 hours. Comparative Example 1 In the implementation of the weave, the organic compound was produced in the same manner except that the comparative compound i was used as the dopant material instead of the compound m6. Hole element. The obtained element was subjected to a current test, and as a result, a blue light emission with a light-emitting efficiency of 79 cd/A and a light-emitting luminance of 79 〇cd/m was obtained at a voltage of 6 8 V and a current density of 10 mA/cm 2 (luminous maximum wavelength: 53. A continuous DC current test with an initial luminance of 3000 cd/m results in a half life of 1300 hours.

Industrial Applicability As described in detail above, the organic EL device using the amino onion derivative of the present invention has high luminous efficiency, and is not easily deteriorated even when used for a long period of time, and has a long life. Therefore, it can be used as a bright green luminescent material for a planar illuminator of a wall-mounted television or display. 153939.doc -49-

Claims (1)

201136910 VII. Patent application scope: 1. An amine-based hydrazine derivative represented by the following formula (丨) [Chemical Formula 1] Wherein R represents a hydrogen atom, a self-primed atom, a substituted or unsubstituted ring to form an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted ring, and a heterocyclic group having 5 to 50 atoms. , substituted or unsubstituted carbon number 1 to alkyl, substituted or unsubstituted cycloalkyl group having 3 to 5 carbon atoms, substituted or unsubstituted carbon number 别~ alkoxy group a substituted or unsubstituted ring forming a broken number of aryl groups, a substituted or unsubstituted ring to form an aryloxy group having 6 to 50 carbon atoms, a substituted or unsubstituted ring to form a carbon number of 6 to 5 An arylthio group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 5 carbon atoms, a substituted or unsubstituted aryl group and/or an alkyl decyl group, a carboxyl group, an amine group, a cyano group, a sulfo group or a meridine group; an integer of m4l~8. When the claw is 2 or more, the plurality of cores may be the same or different; ΑΓΐ~ΑΓ4 are independently formed into a carbon number by a substituted or unsubstituted ring. 6 5〇 aryl, substituted or unsubstituted alkyl having 1 to 50 carbon atoms, substituted or unsubstituted k ring to form a cycloalkyl group having 3 to 5 carbon atoms a substituted or unsubstituted disubstituted ring; an alkyl group having a carbon number of 7 to 50; or a substituted or unsubstituted ring to form a heterocyclic group having 5 to 50 atoms; wherein, Ar丨~8 "Medium! The above is the base represented by the following formula (2), (3) or (4): [Chemical 2] 153939.doc 201136910 (wherein 'X is oxygen (oxime), sulfur (s) or magnetic (Se), R2 is a hydrogen atom, a substituted or unsubstituted ring forms an aryl group having 6 to 60 carbon atoms, substituted or unsubstituted a plurality of alkyl groups of 1 to 50, a substituted or unsubstituted carbon number of 2 to 5 Å, an amine group, a substituted or unsubstituted alkoxy group having a carbon number of i to 5 Å, substituted or The unsubstituted ring forms an aryloxy group having a carbon number of 6 to 5 Å, a substituted or unsubstituted ring to form an arylthio group having a carbon number of 6 to 50, and a substituted or unsubstituted carbon number of 1 to 50. Alkoxycarbonyl, halogen atom, cyano group, nitro group, hydroxyl group, substituted or unsubstituted aryl group and/or alkyl decyl group or carboxyl group; η is an integer of 1 to 7, when 〇 is 2 or more, The plurality of rulers 2 may be the same or different, and in the case of & plural, they may be mutually bonded, 'α to form a saturated or unsaturated, divalent group which may be substituted; R2 is bonded to a 5-membered ring portion containing X. 2. An amine-based hydrazine derivative as claimed in the above formula (1), wherein hydrazine and Ah are in the above formula (2), (3) or (4) The basis of expression. The amine-based onion derivative of the request, which is represented by the above (4). 4. The amine-based tomb derivative of the above formula, wherein the above formula (2 X is an oxygen atom. w 5· An amine-based tomb derivative of the present invention, wherein the above formula (1) is represented by the following formula (6): [Chem. 3] I53939.doc S • 2-201136910 6. 7. 8. 9. 10 11. 4 is the same as above, Rn and Ru are the same as & respectively - the amine hydrazine derivative of the formula 5, wherein in the above formula (the one is bonded thereto, 1 Ar2 is bonded thereto, and the bond at the 6 position is visible. The amine-based hydrazine derivative of claim 5, wherein _NAriAr2 is bonded to the 9th position of the onion group of the above formula (6), and the amine onion derivative of the soil item 1 is bonded to the organic group. A two-component luminescent material, which is an organic electroluminescent device using the amine-based ruthenium derivative doping material of claim 1. A = organic electroluminescent device, which is comprised between the cathode and the anode An organic film layer containing one or more layers of a light-emitting layer, and the light-emitting layer contains the amine-based hydrazine derivative as claimed in any one of claims (1) as a single or mixed The organic electroluminescent device of claim 1 , wherein the luminescent layer contains an amino hydrazine derivative as described above and an anthracene derivative of the following formula (4 〇) and the content of the above amine hydrazine derivative 0.1 to 20 weights 0/〇, [Chem. 4] (4 0) (In the formula (40), ' Ri〇i to rig8 respectively represent a hydrogen atom, a substituted or unsubstituted carbon atom of the fluorine atom 丨~1〇, a substituted or unsubstituted carbon number 3 ～10 cyclized, substituted or unsubstituted alkyl having 3 to 30 carbon atoms 153939.doc 201136910 夕院基 ▲ substituted or unsubstituted ring to form carbon number (a) 芳 芳 芳 、 、, 元, Check the substituted or unsubstituted carbon number! ~2〇 of the alkoxy group substituted or not, the disubstituted % form an aryloxy group having a carbon number of 6 to 20, substituted or not taken to form a carbon a 6 to 3 G aryl group, or a substituted or unsubstituted mother to form a heterocyclic group having an atomic number of 5 to 30, and Aru and Af represent a ring having a carbon number of 6 to 3 by substitution = not or ^. A group or a substituted or unsubstituted ring forms a heterocyclic group having an atomic number of 5 to 3 Å). 153939.doc 201136910 IV. Designation of the representative representative: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: ^八•公T(RiXn 153939.doc